2-(4-Chloro­phen­yl)-2-oxoethyl 2-meth­oxy­benzoate

Hoong-Kun Fun; Safra Izuani Jama Asik; B Garudachari; Arun M Isloor; M N Satyanarayan

doi:10.1107/S1600536811021246

. 2011 Jun 18;67(Pt 7):o1687. doi: 10.1107/S1600536811021246

2-(4-Chlorophenyl)-2-oxoethyl 2-methoxybenzoate

Hoong-Kun Fun ^a,^*,^‡, Safra Izuani Jama Asik ^a, B Garudachari ^b, Arun M Isloor ^b, M N Satyanarayan ^c

PMCID: PMC3151969 PMID: 21837084

Abstract

In the title compound, C₁₆H₁₃ClO₄, the two benzene rings make a dihedral angle of 86.38 (8)°. In the crystal, intermolecular C—H⋯O hydrogen bonds link the molecules to form columns along the a axis. The molecules are also stabilized by a π–π stacking interaction, with a centroid–centroid distance of 3.7793 (10) Å between the inversion-related benzene rings.

Related literature

For general background to phenacyl benzoates, see: Rather & Reid (1919 ▶); Sheehan & Umezaw (1973 ▶); Ruzicka et al. (2002 ▶); Litera et al. (2006 ▶). For applications and synthesis of oxazoles, imidazoles and benzoxazepines, see: Huang et al. (1996 ▶); Gandhi et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₆H₁₃ClO₄
M _r = 304.71
Orthorhombic,
a = 7.7207 (6) Å
b = 14.4411 (12) Å
c = 26.064 (2) Å
V = 2906.0 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 296 K
0.51 × 0.29 × 0.19 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.829, T _max = 0.950
16215 measured reflections
4027 independent reflections
2731 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.116
S = 1.02
4027 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021246/is2727sup1.cif

e-67-o1687-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021246/is2727Isup2.hkl

e-67-o1687-Isup2.hkl^{(197.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811021246/is2727Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1ⁱ	0.93	2.40	3.301 (2)	164

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Symmetry code: (i) Inline graphic .

Acknowledgments

HKF and SIJA thank Universiti Sains Malaysia for the Research University Grants (Nos. 1001/PFIZIK/811160 and 1001/PFIZIK/811151). AMI is grateful to the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India for the Young Scientist award. BG thanks the Department of Information Technology, New Delhi, India for financial support.

supplementary crystallographic information

Comment

Phenacyl benzoate derivatives are very important in identification of organic acids (Rather & Reid, 1919) as they undergo photolysis in neutral and mild conditions (Sheehan & Umezaw, 1973; Ruzicka et al., 2002 ; Litera et al., 2006). They find applications in the field of synthetic chemistry for the synthesis of oxazoles, imidazoles (Huang et al., 1996) and benzoxazepines (Gandhi et al., 1995). The phenacyl esters are usually prepared by reaction between acids with phenacylbromide derivatives in DMF using sodium or potassium carbonate as base. We hereby report the crystal structure of 2-(4-chlorophenyl)-2-oxoethyl 2-methoxybenzoate, (I), which has potential commercial importance.

In the title compound of (I), the bond lengths (Allen et al., 1987) and angles show the normal values. The two benzene rings (C1–C6 and C10–C15) make a dihedral angle of 86.38 (8)°.

In the crystal packing (Fig. 2), intermolecular C2—H2A···O1 hydrogen bonds (Table 1) link the molecules to form columns down to the a-axis. The molecules are also stabilized by π–π stacking interactions between the inversion-related benzene rings (C1–C6 ; centroid Cg1) with a Cg1···Cg1ⁱⁱ separation of 3.7793 (10) Å [symmetry code: (ii) 2 - x, -y, 2 - z].

Experimental

The mixture of 2-methoxybenzoic acid (1.0 g, 0.0065 mol), potassium carbonate (0.98 g, 0.0071 mol) and 2-bromo-1-(4-chlorophenyl)ethanone (1.45 g, 0.0065 mol) in dimethylformamide (10 ml) was stirred at room temperature for 2 h. On cooling, colorless needle-shaped crystals of 2-(4-chlorophenyl)-2-oxoethyl 2-methoxybenzoate begins to separate out. It was collected by filtration and recrystallized from ethanol. Yield : 1.9 g, 95 %, M.p. : 391–392 K, (CAS Registry Number: 282714–31–2).